Strategy for Achieving Long-Wavelength Near-Infrared Luminescence of Diimineplatinum(II) Complexes

Although many strategies have been used to help design effective near-infrared (NIR) luminescent materials, it is still a huge challenge to realize long-wavelength NIR luminescence of diimineplatinum(II) complexes in the solid state. Herein, we have successfully achieved long-wavelength NIR luminescence of a family of diimineplatinum(II) complexes based on a new strategy that combines a one-dimensional (1D) "Pt wire" structure with the electronic effect of the substituent. The structures of six solvated diimineplatinum(II) complexes based on 4,4-dichloro-2,2'-bipyridine or 4,4-dibromo-2,2'-bipyridine and 4-substituted phenylacetylene ligands have been determined, namely, 1·¹/₂toluene, 2·¹/₂THF, 3·¹/₈toluene, 4·¹/₂THF, 5·¹/₈CH₂Cl₂, and 6·¹/₄toluene. All of them crystallize in the monoclinic space group C2/c or C2/m and stack in the 1D "Pt wire" structure. In the solid state, six complexes exhibited unusual long-wavelength metal-metal-to-ligand charge-transfer luminescence that peaked at 984, 1044, 972, 990, 1022, and 935 nm, respectively. Interestingly, 2·¹/₂THF has the shortest Pt···Pt distance and the longest emission wavelength among the six complexes. As far as we know, the luminescence of 2·¹/₂THF at 1044 nm is the longest emission wavelength among known diimineplatinum(II) complexes. Systematic studies revealed that good molecular planarity, suitable substituent position, weak hydrogen-bond-forming ability of the substituents, appropriate molecular bending, and weakening of the interaction between solvated molecules and platinum molecules are conducive to the construction of a 1D "Pt wire" structure of the diimineplatinum(II) complex. Furthermore, the emission energy of the complex is mainly determined by the strength of the Pt-Pt interaction and electronic effect of the substituent.